Thiazine dyestuffs and process of dyeing fibrous material



United States Patent DYESTUFFS AND PROCESS OF DYEING FIBROUS MATERIAL Donald L. Bailey, Snyder, and Ronald M. Pike, Grand Island, N.Y., assignors to Union Carbide Corporation, a corporation of New York I No Drawing. Filed Apr. 29, 1957, Ser. No. 655,502

12 Claims. (Cl. 8-8) This invention relates to silicon-containing dyestuffs as new compositions of matter, and to processes for producing them. More particularly this invention is concerned with silicon-containing thiazine dyestuffs.

The silicon-containing thiazine dyestufis of this invention contain the unit represented by the general formula:

wherein Ar represents a thiazine nucleus and including a substituted thiazine nucleus; X represents a hydrogen atom, or an alkyl radical such as methyl, ethyl, propyl and the like or a C,,H SiE radical; and (a) is an integer having a value of at least 3 and preferably of from 3 to about 5.

The thiazine dyestuffs herein disclosed and claimed contain units which can be represented by the following general formula:

wherein X and (a) have the same meanings as hereinbefore indicated; R represents a hydrogen atom, an alkyl radical, such as methyl, ethyl, propyl and the like, or an alkoxy radical, such as methoxy, ethoxy, propoxy and the like; R represents a hydrogen atom, an alkyl radical, an alkoxy radical, or a sulfo radical, and the like; and R" represents a hydrogen atom or an alkyl radical.

The silicon-containing thiazine dyestufis of this invention are produced by oxidizing a mixture comprising a para-aminoaniline, such as N,N-dimethyl-p-phenylene diamine, an arylaminoalkylsilane and a metal thiosulfate, such as sodium thiosulfate, with a mineral acid solution of an alkali metal dichromate, such as sodium dichromate or potassium dichromate, in the presence of zinc chloride. A large number of thiazine dyestuffs have been produced in the past but none, to our knowledge, have been produced having a silicon-containing group in the molecule.

The para-amin0anilines suitable for use as starting materials in this invention can be represented by the structural formula:

wherein R and R" have the same meanings hereinbefore indicated. In producing the tbiazine dyestuffs, the paraaminoaniline is thiosulfonated to the thiosulfonic acid represented by the general formula:

S-SOs Patented Oct. 11, 1960 at a temperature of from about 20 C. to about 50 C. by oxidation with a mixture of a metal thiosulfate, such as sodium, potassium or aluminum thiosulfate, a mineral acid such as hydrochloric acid or sulfuric acid, and a dichromate such as sodium or potassium dichromate. The arylaminoalkylsilane is added and the mixture is oxidized to the indamine at a temperature of from about 30 C. to about C. It'is known that aluminum sulfate can replace aluminum thiosulfate in this reaction.

The arylaminoalkylsilanes used as starting materials in this invention can be represented by the general formula:

wherein Ar represents an aryl radical or a substituted aryl radical as, for example, a phenyl radical, or lower alkyl, alkoxy, nitro, sulfo, and the like substituted phenyl radicals; X represents a hydrogen atom, an alkyl radical, or an VII radical; V represents an alkyl radical, preferably containing from 1 to about 5 carbon atoms; Y represents an alkoxy radical such as methoxy, ethoxy, propoxy and the like; (a) is an integer having a value of at least 3; and (n) is an integer having a value of from 0 to 3; and wherein the Ar radical is unsubstituted in one meta position and the para position and is reactive.

When a mixture of a non-functional arylaminoalkylsilane and the thiosulfonic acid of the para-aminoaniline are oxidized, the silane thiazine dyestuffs obtained can be represented by the general formula:

wherein R, R, R", V, X, Y, (a) and (n) have the same meanings hereinbefore indicated. However, when a functional arylaminoalkylsilane is used, the dyestuffs obtained are siloxane thiazine dyestuffs containing the unit represented by the general formula:

wherein R, R, R, V and (a) have the same meanings as hereinbefore indicated; X" represents a hydrogen atom, an alkyl radical or a radical; and (b) is an integer having a value of from 0 to 2.

Illustrative of the para-aminoanilines which can be used in this invention are p-phenylenediamine, p-N,N-dirnethylarninoaniline, p-N,N,-diethylaminoaniline, p-N-ethylaminoaniline, 3-methyl-4-N-ethylaminoaniline, 4-N-(psulfobenzylethylamino)-aniline, 2,5-diaminobenzene sulfonic acid and the like.

Suitable arylaminoalkylsilanes are inter alia: N-(gamma-trimethylsilylpropyl)-ani1ine, N-methyl-N- gamm a-trimethylsilylpropyl) -aniline, N,N-digamm a-trimethylsilylpropyl) -aniline,

N-( delta-nimethylsilylbutyl) -2-methoxyaniline,

and the like. v

The arylaminoalkylsilanes and methods for producing them are the subject matter of our copending patent application Serial No. 615,463, filed October 12,1956. These silane intermediates can be produced by reacting an arylamine with an omega-haloalkylsilane at an elevated temperature, as represented by the following general equation:

ar'1 IH+z0.H2.-sli-Ya-..-- Ar' 1 I-C.Hl.-siYa-..+HZ wherein Ar, V, V, Y, (a) and '(n) have the same meanings as hereinbefore indicated and Z reprments a halogen atom. For example, the reaction of molar equivalents of gamma-chloropropyltriethoxysilane with aniline at about 150 C. under an inert gas atmosphere produced N-(gamma-triethoxysilylpropyl)-aniline. By using two molar equivalents of gamma-chloropropyltri- 'ethoxysilane with one mole of aniline there is obtained N,N-di-(gamma-triethoxysilylpropyl)-aniline.

The thiazine dyestuffs of this invention are substantive dried at about 65 C.

to natural fibers such as wool, silk and cotton; and to synthetic fibers such as nylon, acetate, viscose, Dynel, .Acrilan, and the like. In addition they are characteriized by the very useful property of dyeing glass cloth :and silica from aqueous dyebath solutions, giving dyeings of good wash and light fastness properties;

By methods well known in dyestufi technology one can also prepare dyestufis belonging to the safranine class by the oxidation of a mixture of a para-aminoaniline, aniline or a ring substituted aniline and an arylaminoalkylsilane.

i CH:

wvas prepared in the following manner. A 400 ml. glass :flask was equipped with a stirrer, thermometer, dropping funnel and condenser. There was added ml. of 1 N hydrochloric acid and 3.89 g. of N,N-dimethyl-p-'phenylene-diarnine and stirred to complete solution, and then a :solution of 17.5 g. of zinc chloride in 25 ml. of water was added. With efiicient .stirring a solution of 13.5 g. of sodium thiosulfate in 30 ml. of water was added to :the mixture at about 25 C. There was then added to :the flask about /3 of a solution made up to 8 g. of sodium -dichromate in 15 ml. of water and the reaction mixture 'was heated as rapidly as possible to 40 C. A solution -of 7.7 g. of N-methyl-N-(gamma-trierhoxysilylpropyl)- :aniline dissolved in 4 ml. of 37% hydrochloric acid was :added to the flask, and this was followed by the remainder of the sodium dichromate solution. The temperature of :the reaction mixture was raised quickly to 70 C., and then over a 10 minute period to 85 C. After a A hour period the deep blue reaction mixture was cooled to 50 C. and the precipitate which formed was dissolved by the addition of 7.5 ml. of concentrated sulfuric acid. The reaction was allowed to stand at room temperature to precipitate the dyestufi, which was then filtered off, washed on the funnel with Water, and dried in a vacuum oven at 65C. ,for about 24 hours. ,Yield. was 11.7 g. of a deep blue sil'oxane thiazine dye'stutf.

The thiazine dyestu'fi producedwa'ssuitable for dyeing many fibers from a dyebath' coimprising 025 g; of the dyestuff in a mixture-of. 30 m1. of metnanotand 1 mIIor pyridine. The cloths were allowed to stand overnight in the dyebath at room temperature, washed with water, and It is also possible to dye the cloths from an aqueous dyebath at the boil in a shorter period of time. Wool and cotton were dyed a blue-green shade; whereas, silk, nylon, acetate, viscose, and sized and unsized glass cloth wifeldye'd a blue-gray shade.

By substitution of N-(gamma-trimethylsilylpropyD- aniline for the N-methyl-N gama-triethoxysilylpropyl)-aniline, the 'silan'e thiazine 'dye'stutf represented by the following formula was obtained:

What is claimed is: I l. Silicon-containing thiazine dyestuffs containing the unit represented by the general formula:

wherein Ar represents a member selected from the group consisting of a thiazine nucleus and a substituted thiazine nucleus; X represents a member selected from the group consisting of a hydrogen atom, alkyl radicals and radicals; and (a) is an integer having a value of at least 3. v p

2. Silicon-containing thiazine dyestuifs containing the unit represented by the general formula:

wherein R represents a member selected from the group consisting of a hydrogenatom, alkyl radicals and alkoxy radicals; R represents a member selected from the group consisting of ahydrogen atofn, alkyl radicals, alkoxy radicals and sulfo radicals; R" represents a member selected from the group consisting of hydrogen atoms and alkyl radicals; X represents a member selected from the group consisting of a hydrogen atom, alkyl radicals and c.ln.si Yl I radicals; V represents a' member selected fromthe group consisting of alkyl radicals; Y represents a member selected from the group consisting of alkoxy radicals; (a) is an integer having, a value 'ofat least 3; and (n) is an integer having a value of from 0 to 3.

4. Siloxane thiazine dyestufis containing the unit represented by the general formula:

1 b C.Hz.SiO

radicals; V represents a member selected from the group consisting of alkyl radicals; (a) is an integer having a value of at least 3; and (b) is an integer having a value of from to 2.

5. The silane thiazine dyestufi 6. Siloxane thiazine dyestuifs containing the unit represented by the general formula:

7. The method of dyeing fibrous material, which comprises exposing said material to a dyebath containing a silane thiazine dyestufi of claim 3 at an elevated temperature, rinsing, and drying.

8. The method of dyeing fibrous material, which comprises exposing said material to a dyebath containing a. siloxane thiazine dyestufi of claim 4 at an elevated temperature, rinsing, and drying.

9. A fiber dyed with a silane thiazine dyestufi of claim 3.

10. A fiber dyed with a siloxane thiazine dyestufl of claim 4.

11. Glass fiber dyed with a silane thiazine dyestufi of claim 3.

12. Glass fiber dyed with a siloxane thiazine dyestufi of claim 4.

References Cited in the file of this patent UNITED STATES PATENTS 1,766,403 Schulemann June 24, 1930 2,317,965 Bestian et al Apr. 27, 1943 2,715,133 Speier Aug. 9, 1955 2,762,823 Speier Sept. 11, 1956 FOREIGN PATENTS 267,169 Great Britain Mar. 7, 192.7

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,955,898 October 11, 1960 Donald L. Bailey et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 35 to 40, the formula should appear as shown below instead of as lines 46 to 51, the formula should appear as shown below instead of as in the patent:

column 3, line 18, for V read X'-.

Signed and sealed this 23rd day of May 1961.

[SEAL] Attest ERNEST w. SWIDER, DAVID L. LADD,

Attestz'ng Oficer. Oommz'ssz'oner of Patents. 

1. SILICON-CONTAINING THIAZINE DYESTUFFS CONTAINING THE UNIT REPRESENTED BY THE GENERAL FORMULA: 